Zur Koordination von Thiocyanat in ternären Metallkomplexen: CdZn(NCS)₄ und die Kristallstruktur von BaZn(NCS)₄ · 7H₂O / On the Coordination of Thiocyanate in Ternary Metal Complexes: CdZn(NCS)₄ and the Crystal Structure of BaZn(NCS)₄ · 7H₂O

Abstract

<jats:p>CdZn(NCS)<jats:sub>4</jats:sub> (1): studied by means of Precession and Guinier technique. The compound seems to be isomorphous to CdHg(SCN)<jats:sub>4</jats:sub> but with exchanged metal positions consisting of tetrahedral Cd(SCN)<jats:sub>4</jats:sub> and Zn(NCS)<jats:sub>4</jats:sub> groups. (M<jats:sub>r</jats:sub> = 410.1, space group I 4̄, Z = 2, a = 1110.89(2) pm, c = 444.36(2) pm, V = 548.37 · 10<jats:sup>6</jats:sup> pm<jats:sup>3</jats:sup>, d<jats:sub>c</jats:sub> = 2.48 g · cm<jats:sup>-3</jats:sup>.)</jats:p><jats:p>BaZn(NCS)<jats:sub>4</jats:sub>-7H<jats:sub>2</jats:sub>O (2): prepared by reaction of Ba(NCS)<jats:sub>2</jats:sub>-3H<jats:sub>2</jats:sub>O with Zn(NCS)<jats:sub>2</jats:sub> in H<jats:sub>2</jats:sub>O . The crystal structure was solved with X-ray methods. (M<jats:sub>r</jats:sub>= 561.14, space group I 4̄, Z = 8, a = 1894.7(6) pm, c = 1032.4(3) pm, V = 3706.2 · 10<jats:sup>6</jats:sup> pm<jats:sup>3</jats:sup>, λ(AgKa) = 55.83 pm, d<jats:sub>c</jats:sub> = 2.00 g · cm<jats:sup>-3</jats:sup>, μ(AgKa) = 18.89 cm<jats:sup>-1</jats:sup> , F(000) = 2143.8, T = 298 K, final R = 0.0548 for 1475 independent reflections.)</jats:p><jats:p>The structure consists of two crystallographic independent Zn(NCS)<jats:sub>4</jats:sub> tetrahedra, while the Ba<jats:sup>2+</jats:sup> cations are surrounded by 9 oxygen atoms of water molecules and 1 sulfur atom of thiocyanate. The crystal water forms one-dimensional chains, consisting of alternant four- and fivemembered rings.</jats:p>

Investigation of Bimetallic Thiocyanates belonging to ABTC Structure Type: ZnCd(SCN)4 and AHg(SCN)4 (A = Zn, Cd, Mn ) as Nonlinear Optical Crystal Materials

“…AB(SCN) 4 .nH 2 O (where A = Mg, Ca, Sr, Ba, Mn, Fe, Ni, Cu, Zn, Co, Cd, B = Co, Zn, Cd, Hg) series of coordination compounds, are a new field to explore such NLO crystal materials. On the condition that B ≠ Hg, such compounds have received little attention (BRODERSEN et al 1985, MEREITER, PREISINGER 1988. Regarding to the relations between their molecular structures and spectra, the studies were dated from the middle 1960s (FORSTER, GOODGAME 1965, SCAIFE 1967, BAILEY, MICHELSEN 1972.…”